Membrane-assisted Solvent Extraction Research Articles

Ultrasound assisted membrane-assisted solvent extraction for the simultaneous assessment of some drugs involved in drug-facilitated sexual assaults by liquid chromatography-tandem mass spectrometry

A simple and highly efficient ultrasound assisted membrane-assisted solvent extraction (MASE) pre-treatment method for urine has been developed and validated for the simultaneous determination of twenty-two drugs involved in drug-facilitated sexual assaults (DFSAs) by liquid chromatography-tandem mass spectrometry. MASE was performed with 4.0 mL of urine (pH adjusted at 12), 400 μL of hexane as an organic solvent inside the polypropylene membrane, and ultrasonication (45 kHz, 120 W) for 10 min. A pre-concentration factor of 40 was achieved after evaporation (N2 stream) and re-dissolution in 100 µL of methanol. Analytes were separated using a Zorbax Eclipse Plus C18 column under gradient elution with aqueous 10 mM NH4HCO3 (pH 8.0) and methanol as mobile phases. Matrix-matched calibrations allowed the assessment of DFSA drugs of quite different octanol–water partition coefficients (Ko/w), from 1.32 101 for pregabalin to 2.45 105 for clomipramine (Log P values from 1.12 (pregabalin) to 5.39 (clomipramine)). The limit of detection (LOD) was between 0.0075 to 0.37 µg L−1, with analytical recoveries ranging from 73 to 103%, and relative standard deviations (RSDs) within the 2–20% range. The applicability of the method was demonstrated after analysing urine samples under forensic investigation.

Synthetic cathinones determination by liquid chromatography-mass spectrometry after ultrasound membrane assisted extraction

The extraction time for membrane-assisted solvent extraction (MASE) when isolating synthetic cathinones from urine has been speeded up to 30 min by using ultrasounds. Separation and determination of eleven synthetic cathinones was further performed liquid chromatography-tandem mass spectrometry (LC-MS/MS). The ultrasound assisted MASE consisted of adjusting 5.0 mL of urine at pH 11.8 and performing the extractive process with 400 μL of n-hexane as an acceptor phase inside the polypropylene membrane under ultrasonication at room temperature. Synthetic cathinones exhibiting LogP values higher than 2.0, such as 3,4-dimethyl methcathinone, methylendioxypyrovalerone, and naphyrone), were efficiently extracted and pre-concentrated. Other synthetic cathinones (LogP between 2.0 and 0.7) were found to exhibit a lower mass transfer. The method was found to be matrix dependent, and a matrix-matched calibration was required for measurements. The achieved limits of detection (LOD) were between 0.03 (flephedrone) to 0.29 (ethylone) µg L-1, with relative standard deviations (RSDs) within the 6–14% and 7–19% ranges for intraday and inter-day assays, and intraday and inter-day analytical recoveries from 84 to 115% and 85 to 118%, respectively. The developed method was finally applied to urine samples from volunteers attending a music festival.

Membrane assisted process intensification and optimization for removal and recovery of phenol from industrial effluents

The best method of preserving the environment is not to discharge any contaminant but to recover them as value from the effluent streams thereby adopting circular economy. This calls for developing new strategies including intensification of conventional processes to make the recovery of contaminants cost effective and environmentally friendly. In this context, experimental studies are reported with respect to conventional solvent extraction and membrane assisted solvent extraction for recovering phenol from effluent streams. Initial studies are carried out with aqueous solutions of phenol with concentrations up to 500 mg/L using hydrophobic polyvinylidene fluoride based hollow fiber membrane element in tandem with conventional solvent extraction using 1- hexanol as solvent. The operating parameters for the membrane assisted solvent extraction were optimized in parallel with conventional solvent extraction using the statistical tool, response surface methodology to provide a comparative assessment highlighting the advantages of membrane assisted solvent extraction in terms of energy consumption, operational simplicity and environmental friendliness. The studies were validated using real effluents obtained from a formaldehyde resin manufacturer. The comparative study highlights the specific advantages and demonstrates the superiority of membrane assisted solvent extraction using a real industrial effluent. It was observed that more than 98 % of phenol could be removed from effluent in membrane assisted solvent extraction and recover about 90 %, continuously allowing the recycle of the solvent. Being closed loop operation, no solvent is exposed to the environment making the process environmentally friendly operation. The mechanism of mass transfer in membrane contactors follows resistance in series model and the experimental values of mass transfer coefficient were estimated to be between 1.7 × 10 −7 and 2.2 × 10 −7 m/s, whereas the empirical values were around 1.3 × 10 −7 m/s.

Source apportionment of PM10 and health risk assessment related in a narrow tropical valley. Study case: Metropolitan area of Aburrá Valley (Colombia)

This study investigates spatio-temporal variations of PM10 mass concentrations and associated metal(oid)s, δ13C carbon isotope ratios, polycyclic aromatic hydrocarbons (PAHs), total organic carbon (TOC) and equivalent black carbon (eBC) concentrations over a half year period (from March 2017 to October 2017) in two residential areas of Medellín (MED-1 and MED-2) and Itagüí municipality (ITA-1 and ITA-2) at a tropical narrow valley (Aburrá Valley, Colombia), where few data are available. A total of 104 samples were analysed by using validated analytical methodologies, providing valuable data for PM10 chemical characterisation. Metal(oid)s concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion, and PAHs concentrations were measured by Gas Chromatography-Mass Spectrometry (GC–MS) after Pressurised Hot Water Extraction (PHWE) and Membrane Assisted Solvent Extraction (MASE). Mean PM10 mass concentration ranged from 37.0 µg m−3 to 45.7 µg m−3 in ITA-2 and MED-2 sites, respectively. Al, Ca, Mg and Na (from 6249 ng m−3 for Mg at MED-1 site to 10,506 ng m−3 for Ca at MED-2 site) were the major elements in PM10 samples, whilst As, Be, Bi, Co, Cs, Li, Ni, Sb, Se, Tl and V were found at trace levels (< 5.4 ng m−3). Benzo[g,h,i] perylene (BghiP), benzo[b + j]fluoranthene (BbjF) and indene(1,2,3-c,d)pyrene (IcdP) were the most profuse PAHs in PM10 samples, with average concentrations of 0.82–0.86, 0.60–0.78 and 0.47–0.58 ng m−3, respectively. Results observed in the four sampling sites showed a similar dispersion pattern of pollutants, with temporal fluctuations which seems to be associated to the meteorology of the valley. A PM source apportionment study were carried out by using the positive matrix factorization (PMF) model, pointing to re-suspended dust, combustion processes, quarry activity and secondary aerosols as PM10 sources in the study area. Among them, combustion was the major PM10 contribution (accounting from 32.1 to 32.9% in ITA-1 and ITA-2, respectively), followed by secondary aerosols (accounting for 13.2% and 23.3% ITA-1 and MED-1, respectively). Finally, a moderate carcinogenic risk was observed for PM10-bound PAHs exposure via inhalation, whereas significant carcinogenic risk was estimated for carcinogenic metal(oid)s exposure in the area during the sampling period.

Isolation and quantification of synthetic cannabinoid receptor agonists in human urine using membrane-assisted solvent extraction followed by liquid chromatography-tandem mass spectrometry.

The global market for new psychoactive substances (NPSs) continues to expand, and the range of drugs available on the market has probably never been wider. Synthetic cannabinoids (SCRAs) constitute the largest family of NPSs, and they go unnoticed during illicit drug market control and during routine toxicological-forensic analysis. Membrane-assisted solvent extraction (MASE) has been a novelty proposed for the simultaneous extraction of SCRAs, and urine has been selected as a model forensic-clinical sample. Isolated SCRAs were further determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). An optimised sample pre-treatment procedure consists of using 400 μL of n-hexane as an extraction phase placed inside a polypropylene (PP) membrane, adjusting the donor phase (urine) at a pH value of 5.9. Extraction was assisted by mechanical (orbital-horizontal) stirring in a temperature-controlled chamber at room temperature for 20 min. n-Hexane extracts were evaporated to dryness and re-suspended in 100 μL of mobile phase, which leads to a pre-concentration factor of 50. Method validation showed analytical recoveries higher than 80% for most SCRAs and repeatability (inter-day and intra-day assays) with RSD values lower than 20%. The proposed method was found to be selective and sensitive and limits of quantification (LOQs) between 0.10 and 1.0 μg L-1 were achieved.

The Varietal Influence of Flavour Precursors from Grape Marc on Monoterpene and C13-Norisoprenoid Profiles in Wine as Determined by Membrane-Assisted Solvent Extraction (MASE) GC-MS.

The winemaking by-product grape marc (syn. pomace) contains significant quantities of latent flavour in the form of flavour precursors which can be extracted and used to modulate the volatile composition of wine via chemical hydrolysis. Varietal differences in grapes are widely known with respect to their monoterpene content, and this work aimed to extend this knowledge into differences due to cultivar in volatiles derived from marc precursors following wine-like storage conditions. Marc extracts were produced from floral and non-floral grape lots on a laboratory-scale and from Muscat Gordo Blanco marc on a winery -scale, added to a base white wine for storage over five to six months, before being assessed using a newly developed membrane-assisted solvent extraction gas chromatography-mass spectrometry (GC-MS) method. The geraniol glucoside content of the marc extracts was higher than that of juices produced from each grape lot. In all wines with added marc extract from a floral variety, geraniol glucoside concentration increased by around 150–200%, with increases also observed for non-floral varieties. The relative volatile profile from extracts of the floral varieties was similar but had varied absolute concentrations. In summary, while varietally pure extracts would provide the greatest control over flavour outcomes when used in winemaking, aggregated marc parcels from floral cultivars may provide a mechanism to simplify the production logistics of latent flavour extracts for use in the wine sector.

Performance of membrane assisted solvent extraction with homologous solvents for the removal and recovery of phenol

Performance of membrane assisted solvent extraction with homologous solvents for the removal and recovery of phenol

Current status and future prospects of membrane separation processes for value recovery from wastewater

Resource constraints and deteriorating environment have made it necessary to look for intensification of the industrial processes, to recover value from spent streams for reuse. The development of reverse osmosis has already established that water can be recovered from aqueous streams in a cost-effective and beneficial manner to the industries. With the development of several membrane processes and membrane materials, the possibility of recovering value from the effluents looks like a workable proposition. In this context, the potentialities of the different membrane processes in value recovery are presented. Among the pressure-driven processes, reverse osmosis can be used for the recovery of water as value. Nanofiltration has been used for the recovery of several dyes including crystal violet, congo red, methyl blue, etc., while ultrafiltration has been used in the fractionation of different solute species using membranes of different pore-size characteristics. Diffusion dialysis is found useful in the separation of acids from its salt solutions. Bipolar membrane electrodialysis has the potential to regenerate acid and base from salt solutions. Thermally driven membrane distillation can provide desalinated water, besides reducing the temperature of hot discharge streams. Passive membrane processes such as supported liquid membranes and membrane-assisted solvent extraction have been found useful in separating minor components from the wastewater streams. The details are discussed to drive home that membrane processes can be useful to achieve the objectives of value recovery, in a cost-effective manner through process intensification, as they are more compact and individual streams can be treated and value used seamlessly.

Multivariate optimization of a two-way technique for extraction of pharmaceuticals in surface water using a combination of membrane assisted solvent extraction and a molecularly imprinted polymer

This work demonstrates development and evaluation of a two-way technique based on the combination of membrane assisted solvent extraction and a molecularly imprinted polymer (MASE-MIP) for selective and efficient extraction of five selected pharmaceuticals belonging to five different therapeutic classes. The pharmaceuticals were extracted from surface water samples followed by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-qTOF/MS) determination. A central composite design was applied to optimize the influence of the sample salt content, the stirring rate, the stirring time and the amount of MIP on the extraction of an anticonvulsant (carbamazepine), a cardiac stimulant (etilefrine), a muscle relaxant (methocarbamol), an antiretroviral (nevirapine) and an antidepressant (venlafaxine) from surface water. Optimization of the analytical method was performed by spiking water with a mixture of all five pharmaceuticals at 500 ng mL−1. Optimum extraction conditions for a sample volume of 18 mL were found to be 5 g of salt content, a stirring rate of 400 rpm, an extraction time of 60 min and 50 mg of MIP. The MASE-MIP-LC-qTOF/MS method gave detection and quantification limits ranging from 0.09 to 0.20 ng mL−1 and 0.31–0.69 ng mL−1, respectively. The spiked river water samples yielded recoveries ranging from 38 to 91% for the selected model compounds belonging to the five classes of pharmaceuticals. Upon the application of the developed analytical method in water analysis, all selected pharmaceuticals were detected in South African river water with nevirapine and venlafaxine being more prominent attaining the maximum concentrations of 1.64 and 2.48 ng mL−1, respectively.

Polycyclic aromatic hydrocarbons analysis in tea infusions and tea beverages using membrane assisted solvent extraction

Membrane Assisted Solvent Extraction (MASE) was applied as an extraction and enrichment technique of polycyclic aromatic hydrocarbons (PAHs) from tea infusions and fruit/herbal-tea beverages. PAHs have been separated and detected by high performance liquid chromatography coupled to a fluorescence detector (HPLC-FLD). Variables affecting MASE comprising extraction temperature and time, stirring rate, acceptor solvent (hexane) volume, organic modifier in the donor phase (methanol) volume, aqueous donor phase pH and ionic strength were simultaneously studied by applying a Plackett–Burman design (PBD) as screening method. Results showed statistical significance for acceptor solvent volume, extraction time and stirring rate, which were optimised by an orthogonal 23 + star central composite design (CCD). Quantitative recoveries for all PAHs (within 78–116%) were obtained by using the optimized extraction conditions: 350 µL of hexane, extraction time of 70 min and stirring rate of 175 rpm. Extraction temperature, ionic strength and donor phase pH were statistically non-significant, which simplify the procedure. The MASE method has been found sensitive (LOQs < 43 ng L−1) and precise (RSDs of < 13%). Finally, the method has been applied to assess PAHs levels in several tea infusions and fruit/herbal-tea beverages in the presence of surrogate standards. The total mean Σ16PAHs in tea infusions were from 1.2 ng L−1 (white tea) to 151.7 ng L−1 (black tea), while total mean Σ16PAHs was lower than 11.5 ng L−1 regarding tea fruit/herbal beverages. Furthermore, benzo(a)pyrene (BaP) concentrations were from < 1.5 ng L−1 (white tea) to 4.6 ng L−1 (green tea). Nevertheless, BaP concentrations obtained as well as the summation of BaA, Chry, BbF and BaP concentrations (4.6 ng L−1 for tea beverages to 7.5 ng L−1 for green tea infusions) did not exceeded the maximum levels according with European Union (EU) standards. Finally, BaP carcinogenic equivalent concentration (BaPeq) and BaP mutagenic equivalent concentration (BaPMeq) were estimated, ranging from 0.01 ng L−1 to 19.8 ng L−1 and 0.23 ng L−1 to 6.9 ng L−1, respectively.

Effective separation of toxic phenol from aquatic system using membrane assisted solvent extraction system

Effective separation of toxic phenol from aquatic system using membrane assisted solvent extraction system

Determination of atmospheric particle-bound polycyclic aromatic hydrocarbons using subcritical water extraction coupled with membrane microextraction

A green analytical methodology for the determination of 16 priority polycyclic aromatic hydrocarbons (PAHs) and 8 related compounds in air particulate matter was developed and validated. The method was based on pressurized hot water extraction (PHWE) followed by miniaturized membrane-assisted solvent extraction (MASE) and programmed temperature vaporization-gas chromatography-ion trap tandem mass spectrometry detection (PTV-GC–MS/MS). The parameters studied for PHWE were percentage of organic modifier (25% MeOH), temperature (200 °C) and static extraction time (5 min). For MASE, extraction temperature (30 °C), time (90 min) and effect of an organic modifier were also optimized. The matrix effect was evaluated and compensated using deuterated labelled standards as surrogates for the quantitation of the target compounds. The analytical performance of the method was satisfactory: relative recoveries varied between 78 and 118% and repeatability and intermediate precision were <22% for all compounds. The Method Quantitation Limits (MQL) ranged from 0.9 (TPY) to 75.6 pg m−3 (NAP). Satisfactory results for accuracy and traceability were evidenced by the analysis of a reference material (SRM 1649b) and comparison with previously published methods. The greenness score was estimated and compared with other techniques widely used for the analysis of PAHs in particulate matter, having a lower relative environmental impact.

Development of a single format membrane assisted solvent extraction-molecularly imprinted polymer technique for extraction of polycyclic aromatic hydrocarbons in wastewater followed by gas chromatography mass spectrometry determination

A technique that combines membrane assisted solvent extraction and molecularly imprinted polymer into a single step format has been successfully developed and evaluated for the extraction of the 16 US-EPA priority polycyclic aromatic hydrocarbons in wastewater samples followed by determination using gas chromatography coupled with time of flight mass spectrometry. The technique involves placing the polymer particles into a hydrophobic polypropylene membrane bag which is in contact with an aqueous donor phase. The technique was optimized for various parameters that include presence of an organic modifier in the donor phase, stirring rate and extraction time. The optimum conditions were 25% of dimethyl sulfoxide as an organic modifier and stirring at 1000 rpm for 120 min. The limits of detection using the technique were in the 0.01–0.45 ng mL−1 range. Linearity values determined in the 10–1 000 ng mL−1 calibration range were all above 0.9972. Extraction efficiencies of the sixt analytes calculated as averages for three spiking concentrations ranged from 62.8 to 96.8% (RSD = 3.1–12.3%). The optimized method was tested for the extraction of polycyclic aromatic hydrocarbons in wastewater samples in the presence of surrogate standards. The developed method showed great reproducibility with inter day repeatability values ranging from 0.6 to 24.9%. The analytes were quantified in the nanogram level showing that the developed technique is a viable alternative in the analysis of trace organic compounds in complex aqueous samples.

Membrane-assisted extraction of monoterpenes: from in silico solvent screening towards biotechnological process application.

This work focuses on the process development of membrane-assisted solvent extraction of hydrophobic compounds such as monoterpenes. Beginning with the choice of suitable solvents, quantum chemical calculations with the simulation tool COSMO-RS were carried out to predict the partition coefficient (logP) of (S)-(+)-carvone and terpinen-4-ol in various solvent–water systems and validated afterwards with experimental data. COSMO-RS results show good prediction accuracy for non-polar solvents such as n-hexane, ethyl acetate and n-heptane even in the presence of salts and glycerol in an aqueous medium. Based on the high logP value, n-heptane was chosen for the extraction of (S)-(+)-carvone in a lab-scale hollow-fibre membrane contactor. Two operation modes are investigated where experimental and theoretical mass transfer values, based on their related partition coefficients, were compared. In addition, the process is evaluated in terms of extraction efficiency and overall product recovery, and its biotechnological application potential is discussed. Our work demonstrates that the combination of in silico prediction by COSMO-RS with membrane-assisted extraction is a promising approach for the recovery of hydrophobic compounds from aqueous solutions.

Development and optimisation of a novel three-way extraction technique based on a combination of Soxhlet extraction, membrane assisted solvent extraction and a molecularly imprinted polymer using sludge polycyclic aromatic hydrocarbons as model compounds.

A novel technique that integrates extraction and clean-up into a single step format is reported as part of the search for new sample preparation techniques in the analysis of persistent organic pollutants from complex samples. This was achieved by combining the extraction efficiency of the Soxhlet extractor, the selectivity of a size exclusion membrane and the specificity of a molecularly imprinted polymer for the extraction of polycyclic aromatic hydrocarbons from wastewater sludge followed by quantitation using gas chromatography with time-of-flight mass spectrometry. The approach is described as the Soxhlet extraction membrane-assisted solvent extraction molecularly imprinted polymer technique. This technique was optimised for various parameters such as extraction solvent, reflux time and membrane acceptor phase. The applicability of the developed technique was optimised using a wastewater sludge certified reference material and then tested on real wastewater sludge samples. The method detection limits ranged from 0.14 to 12.86ng/g with relative standard deviation values for the extraction of the 16 US-EPA priority polycyclic aromatic hydrocarbons from wastewater sludge samples ranging from 0.78 to 18%. The extraction process was therefore reproducible and showed remarkable selectivity. The developed technique is a promising prospect that can be applied in the analysis of organic pollutants from complex solid samples.

Selective Extraction of Rare Earth Elements from Permanent Magnet Scraps with Membrane Solvent Extraction.

The rare earth elements (REEs) such as neodymium, praseodymium, and dysprosium were successfully recovered from commercial NdFeB magnets and industrial scrap magnets via membrane assisted solvent extraction (MSX). A hollow fiber membrane system was evaluated to extract REEs in a single step with the feed and strip solutions circulating continuously through the MSX system. The effects of several experimental variables on REE extraction such as flow rate, concentration of REEs in the feed solution, membrane configuration, and composition of acids were investigated with the MSX system. A multimembrane module configuration with REEs dissolved in aqueous nitric acid solutions showed high selectivity for REE extraction with no coextraction of non-REEs, whereas the use of aqueous hydrochloric acid solution resulted in coextraction of non-REEs due to the formation of chloroanions of non-REEs. The REE oxides were recovered from the strip solution through precipitation, drying, and annealing steps. The resulting REE oxides were characterized with XRD, SEM-EDX, and ICP-OES, demonstrating that the membrane assisted solvent extraction is capable of selectively recovering pure REEs from the industrial scrap magnets.

Evaluation of preconcentration methods in the analysis of synthetic musks in whole‐water samples

According to the European Water Framework Directive, environmental assessment of organic compounds should be made in whole-water samples, but due to their hydrophobicity and strong attraction to organic content these compounds can be found bound to suspended particle matter or in the dissolved fraction. In this work, the extraction of musk compounds was studied in whole-water samples exhibiting different amounts of dissolved organic carbon and suspended particulate matter using polyethersulfone preconcentration technique. Matrix effects in estuarine and wastewater (both influent and effluent) were evaluated for filtered and unfiltered samples. For unfiltered samples, estuarine water exhibited matrix effects <20%, while for effluent it was up to 48% and for influent ranged from 85 to 99%. To compensate matrix effects and determine total concentrations in unfiltered samples, different quantification approaches were tested: the use of deuterated analogues and standard additions. Standard additions provided the best results for unfiltered samples. Finally, filtered and unfiltered samples were analyzed using both polyethersulfone preconcentration and membrane-assisted solvent extraction and results showed a good agreement between the two methods. In both cases unfiltered samples provided concentrations 1.5-2.6 times higher than filtered samples.

Pressurized hot water extraction followed by miniaturized membrane assisted solvent extraction for the green analysis of alkylphenols in sediments

A novel and Green analytical methodology for the determination of alkylphenols (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol) in sediments was developed and validated. The method was based on pressurized hot water extraction (PHWE) followed by miniaturized membrane assisted solvent extraction (MASE) and liquid chromatography–electrospray ionization tandem mass spectrometry detection (LC–ESI-MS/MS). The extraction conditions were optimized by a Plackett–Burman design in order to minimize the number of assays according to Green principles. Matrix effect was studied and compensated using deuterated labeled standards as surrogate standards for the quantitation of the target compounds. The analytical features of the method were satisfactory: relative recoveries varied between 92 and 103% and repeatability and intermediate precision were <9% for all compounds. Quantitation limits of the method (MQL) ranged from 0.061 (4-n-nonylphenol) to 1.7ngg−1 dry weight (nonylphenol). Sensitivity, selectivity, automaticity and fastness are the main advantages of the exposed methodology. Reagent consumption, analysis time and waste generation were minimized. The “greenness” of the proposed method was evaluated using an analytical Eco-Scale approach and satisfactory results were obtained. The applicability of the proposed method was demonstrated analysing sediment samples of Galicia coast (NW of Spain) and the ubiquity of alkylphenols in the environment was demonstrated.

Simultaneous analysis of polychlorinated biphenyls and organochlorine pesticides in seawater samples by membrane-assisted solvent extraction combined with gas chromatography-electron capture detector and gas chromatography-tandem mass spectrometry.

A highly efficient and environment-friendly membrane-assisted solvent extraction system combined with gas chromatography-electron capture detector was applied in the simultaneous determination of 17 polychlorinated biphenyls and organochlorine pesticides in seawater samples. Variables affecting extraction efficiency, including extraction solvent used, stirring rate, extraction time, and temperature, were optimized extensively. Under optimal extraction conditions, recoveries between 76.9% and 104.6% in seawater samples were achieved, and relative standard deviation values below 10% were obtained. The limit of detection (signal-to-noise ratio=3) and limit of quantification (signal-to-noise ratio=10) of 17 polychlorinated biphenyls and organochlorine pesticides in seawater ranged from 0.14ngL(-1) to 0.36ngL(-1) and 0.46ngL(-1) to 1.19ngL(-1), respectively. Matrix effects on extraction efficiency were evaluated by comparing with the results obtained using tap water. The extraction effect of developed membrane-assisted solvent extraction method was further demonstrated by gas chromatography-tandem mass spectrometry which can provide structural information of the analytes for more accurate identification, and results identical to those produced by gas chromatography-electron capture detector were obtained. These findings demonstrate the applicability of the developed membrane-assisted solvent extraction determination method for coupling to gas chromatography-electron capture detector or tandem mass spectrometry for determining polychlorinated biphenyls and organochlorine pesticides in seawater samples.

Matrix effect during the membrane-assisted solvent extraction coupled to liquid chromatography tandem mass spectrometry for the determination of a variety of endocrine disrupting compounds in wastewater

Membrane-assisted solvent extraction (MASE) coupled to liquid chromatography–triple quadrupole mass spectrometry (LC–MS/MS) was studied for the determination of a variety of emerging and priority compounds in wastewater. Among the target analytes studied certain hormones (estrone (E1), 17β-estradiol (E2), androsterone (ADT), 17α-ethynyl estradiol (EE2), diethylstilbestrol (DES), equilin (EQ), testosterone (TT), mestranol (MeEE2), 19-norethisterone (NT), progesterone (PG) and equilenin (EQN)), alkylphenols (APs) (4-tert-octylphenol (4tOP), nonylphenol technical mixture (NPs) and 4n-octylphenol (4nOP)) and BPA were included. The work was primarily focused in the LC–MS/MS detection step, both in terms of variable optimization and with respect to the matrix effect study. Both, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) were assessed both in the negative and positive mode, including the optimization of MS/MS operating conditions. The best results were obtained, in most of the cases, for ESI using 0.05% ammonium hydroxide as buffer solution in the mobile phase, composed with methanol and water. Under optimum detection conditions, matrix effect during the detection step was thoroughly studied. Dilution, correction with deuterated analogues and clean-up of the extracts were evaluated for matrix effect correction. Clean-up with Florisil together with correction with deuterated analogues provided the most satisfactory results, with apparent recoveries in the 57–136% range and method detection limits in the low ngL−1 level for most of the analytes. For further validation of the method, two separated extraction procedures, the above mentioned MASE, and conventional solid phase extraction (SPE) were compared during the analysis of real samples and comparable results were successfully obtained for E1, E2, EE2, DES, NT, TT, EQ, PG, BPA, ADT, 4nOP, 4tOP, NPs and EQN.